US4467098A - Process for the manufacture of substituted 3-hydroxy-1,2,4-triazoles - Google Patents

Process for the manufacture of substituted 3-hydroxy-1,2,4-triazoles Download PDF

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Publication number
US4467098A
US4467098A US06/366,320 US36632082A US4467098A US 4467098 A US4467098 A US 4467098A US 36632082 A US36632082 A US 36632082A US 4467098 A US4467098 A US 4467098A
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Prior art keywords
recited
semicarbazide
acid
mol
water
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Expired - Lifetime
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US06/366,320
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English (en)
Inventor
Manfred Koch
Gerhard Stahler
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Hoechst AG
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Hoechst AG
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Priority claimed from DE19813114316 external-priority patent/DE3114316A1/de
Priority claimed from DE19813114314 external-priority patent/DE3114314A1/de
Application filed by Hoechst AG filed Critical Hoechst AG
Assigned to HOECHST AKTIENGESELLSCHAFT, D-6230 FRANKFURT AM MAIN 80, GERMANY A CORP OF GERMANY reassignment HOECHST AKTIENGESELLSCHAFT, D-6230 FRANKFURT AM MAIN 80, GERMANY A CORP OF GERMANY ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: KOCH, MANFRED, STAHLER, GERHARD
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D249/12—Oxygen or sulfur atoms

Definitions

  • 3-Hydroxytriazoles of the formula I are known intermediates for the manufacture of insecticides (cf. German Pat. Nos. 910,652; 1,299,924; 1,670,876; German Offenlegungsschriften Nos. 2,251,074; 2,251,075; 2,251,096; 2,352,141; 2,352,142).
  • the present invention therefore relates to a process for the manufacture of substituted 3-hydroxy-1,2,4-triazoles by cyclization of correspondingly substituted semicarbazides with formic acid, which comprises carrying out the reaction in the presence of an inorganic or strong organic acid, or their halides or anhydrides.
  • the process according to the invention yields 3-hydroxytriazoles of the formula I ##STR1## which are substituted in position 1.
  • the type of the substituent R is of no importance for a successful reaction, provided that R is inert under the reaction conditions.
  • R is preferably a substituted or unsubstituted aliphatic, cycloaliphatic or aromatic radical.
  • Examples hereof are: (C 1 -C 8 )alkyl, (C 1 -C 4 )alkoxy-(C 1 -C 4 )alkyl, cyano-(C 1 -C 4 )alkyl, halogeno-(C 1 -C 4 )alkyl, (C 3 -C 7 )-cycloalkyl; (C 6 -C 10 )-aryl optionally substituted by one or two substituents selected from the group consisting of (C 1 -C 4 )alkyl, (C 1 -C 4 )alkoxy, (C 1 -C 4 )alkylthio, halogen, trifluoromethyl, cyano, nitro and (C 1 -C 4 )alkoxycarbonyl and benzyl optionally substituted by one or two substituents selected from the group consisting of (C 1 -C 4 )-alkyl, (C 1 -C 4 )alkoxy, halogen and nitro
  • At least the stoichiometric quantity of 1 mol, preferably of 2 to 3 mols, of formic acid, per mol of semicarbazide is required to obtain high yields. Greater quantities are not harmful, but offer no advantages either.
  • Formic acid may be used in undiluted form, preferably, however, an inert solvent or diluent is added.
  • suitable solvents or diluents are water, hydrocarbons such as toluene or xylene, chlorohydrocarbons such as chlorobenzene or carbon tetrachloride, nitriles such as propionitrile or amides such as dimethyl formamide. Water is preferred.
  • the quantity of the inert solvent or diluent is in the range from zero to 500 ml per mol of semicarbazide.
  • Formic acid may be diluted to ten times its original volume, higher dilution degrees are not recommended.
  • water is used as solvent or diluent, the water content should be preferably from 15 to 85%, in particular from 50 to 80%.
  • acids there may be used any known strong acids, in particular sulfuric acid, hydrochloric acid, gaseous hydrogen chloride, chlorosulfonic acid, phosphoric acid and p-toluenesulfonic acid.
  • Suitable acid halides are preferably inorganic acid chlorides and bromides which decompose with the water present to give acids. Examples hereof are: thionyl chloride, sulfuryl chloride, phosphorus trichloride or tribromide, phosphorus pentachloride and phosphorus oxychloride.
  • Phosphorus pentoxide is a suitable acid anhydride.
  • the quantity of these acid additives is preferably in the range from 0.05 to 0.5 mol, in particular from 0.1 to 0.3 mol, per mol of semicarbazide.
  • the reaction temperature should be above 80° C. and may be up to 150° C. if the operation is carried out under pressure. Under normal pressure the reaction temperature is preferably 90° to 100° C.
  • the reaction time depends on the quantity of formic acid and inorganic acid used and is generally in the range of one to 24 hours.
  • the reaction products may be isolated in simple manner by suction-filtering the precipitated triazole. If the content of aqueous formic acid is higher, dilution of the reaction mixture with water prior to work-up is recommended.
  • the mother liquor obtained upon separation of the reaction product can be used for further batches, it being only necessary to replace the quantities of semicarbazide, formic acid and of inorganic acid consumed.
  • the formic acid may be separated from the mother liquor by adding an alcohol and distilling off the ester formed.
  • Formic acid may be further recovered by azeotropic distillation, for example of the azeotropic mixture formic acid/water or formic acid/xylene/water.
  • Formic acid may finally be recovered by extraction from the aqueous solution for example with N,N-dibutyl formamide and subsequent distillation.
  • a further advantage of the process of the invention is that it may be performed together with the process for the manufacture of the semicarbazide used as starting compound in a single vessel.
  • hydrazines especially phenyl hydrazines are, however, blood toxins for warmblooded animals, highly toxic to fish and because of their bactericidal properties are difficult to degrade biologically. The removal of phenyl hydrazines from waste water is therefore difficult to achieve.
  • the manufacture of semicarbazides according to known processes may be combined with their further reaction to the triazoles of formula I by reacting hydrazine (a) with at least an equimolar quantity, preferably a low excess of up to 15 mol% of a cyanate (NaOCN, KOCN, NH 4 OCN) in the pressure of about an equimole quantity of an organic or inorganic acid at 0° to 60° C.
  • hydrazine (a) with at least an equimolar quantity, preferably a low excess of up to 15 mol% of a cyanate (NaOCN, KOCN, NH 4 OCN) in the pressure of about an equimole quantity of an organic or inorganic acid at 0° to 60° C.
  • the total yield is improved and the waste water pollution is reduced by combining both process steps.
  • the hydroxytriazoles of the formula I are obtained in excellent yield and in a high purity, which renders a subsequent purification superfluous for most uses, for example for the production of pesticides. If the process is performed in aqueous or aqueous-organic solutions, technical formic acid (of about 85% concentration) can be used, which is an additional advantage of the invention process.
  • reaction mixture was cooled to 100° C., whereupon 324.7 g (6 mols) of 85% formic acid and 50 g (0.5 mol) of concentrated sulfuric acid were added dropwise.
  • the reaction mixture was stirred for a further 6 hours at 95° C. and cooled and the precipitated 1-phenyl-3-hydroxy-1,2,4-triazole was suction-filtered.
  • Excess formic acid can be recovered from the mother liquor by adding 144 g (4.5 mols) of methanol and distilling off the methyl formate formed (boiling point 32° C.)).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
US06/366,320 1981-04-09 1982-04-07 Process for the manufacture of substituted 3-hydroxy-1,2,4-triazoles Expired - Lifetime US4467098A (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE3114316 1981-04-09
DE19813114316 DE3114316A1 (de) 1981-04-09 1981-04-09 "verfahren zur herstellung von 3-hydroxy-1,2,4-triazolen"
DE19813114314 DE3114314A1 (de) 1981-04-09 1981-04-09 "verfahren zur herstellung von substituierten 3-hydroxy-1,2,4-triazolen"
DE3114314 1981-04-09

Publications (1)

Publication Number Publication Date
US4467098A true US4467098A (en) 1984-08-21

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US06/366,320 Expired - Lifetime US4467098A (en) 1981-04-09 1982-04-07 Process for the manufacture of substituted 3-hydroxy-1,2,4-triazoles

Country Status (6)

Country Link
US (1) US4467098A (xx)
EP (1) EP0062853B1 (xx)
CA (1) CA1183543A (xx)
DE (1) DE3267240D1 (xx)
ES (1) ES8301948A1 (xx)
IL (1) IL65457A (xx)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4927940A (en) * 1989-05-01 1990-05-22 Olin Corporation Process for low chloride 1,2,4-triazol-5-one
US4927740A (en) * 1987-10-26 1990-05-22 Basf Aktiengesellschaft Closing and/or sealing orifices, cavities or spaces in printing plates mounted on plate cylinders
US4999434A (en) * 1987-09-28 1991-03-12 Olin Corporation Process for low chloride 1,2,4-triazol-5-one
US5112983A (en) * 1987-09-28 1992-05-12 Olin Corporation Process for producing 1,2,4-triazol-5-one using organic sulfonic acids and polymers thereof as a catalyst

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2531429A1 (fr) * 1982-08-06 1984-02-10 Rhone Poulenc Agrochimie Procede de preparation d'hydroxy-triazoles utilisables comme intermediaires pour les herbicides

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3862124A (en) * 1970-10-22 1975-01-21 Ciba Geigy Corp Triazolylthiophosphoric acid esters
US3862957A (en) * 1971-10-21 1975-01-28 Ciba Geigy Corp 1,2,4-Triazol-3-ol esters

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3625951A (en) * 1970-12-23 1971-12-07 Air Prod & Chem Preparation of 3,4-disubstituted-delta-2-1,2,-triazoline-5-thiones
CH601266A5 (xx) * 1974-08-29 1978-06-30 Ciba Geigy Ag
US4055572A (en) * 1975-08-06 1977-10-25 Ciba-Geigy Corporation Process for the production of 3-hydroxy-1,2,4-triazole derivatives

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3862124A (en) * 1970-10-22 1975-01-21 Ciba Geigy Corp Triazolylthiophosphoric acid esters
US3862957A (en) * 1971-10-21 1975-01-28 Ciba Geigy Corp 1,2,4-Triazol-3-ol esters

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Widman et al., Ber. Deut. Chem. Gesel., vol. 26, pp. 2612 2617, (1893). *
Widman et al., Ber. Deut. Chem. Gesel., vol. 26, pp. 2612-2617, (1893).

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4999434A (en) * 1987-09-28 1991-03-12 Olin Corporation Process for low chloride 1,2,4-triazol-5-one
US5112983A (en) * 1987-09-28 1992-05-12 Olin Corporation Process for producing 1,2,4-triazol-5-one using organic sulfonic acids and polymers thereof as a catalyst
US4927740A (en) * 1987-10-26 1990-05-22 Basf Aktiengesellschaft Closing and/or sealing orifices, cavities or spaces in printing plates mounted on plate cylinders
US4927940A (en) * 1989-05-01 1990-05-22 Olin Corporation Process for low chloride 1,2,4-triazol-5-one
WO1990013543A1 (en) * 1989-05-01 1990-11-15 Olin Corporation Improved process for low chloride 1,2,4-triazol-5-one

Also Published As

Publication number Publication date
EP0062853A2 (de) 1982-10-20
ES511107A0 (es) 1983-02-01
CA1183543A (en) 1985-03-05
EP0062853B1 (de) 1985-11-06
ES8301948A1 (es) 1983-02-01
EP0062853A3 (en) 1983-08-17
IL65457A (en) 1985-07-31
IL65457A0 (en) 1982-07-30
DE3267240D1 (en) 1985-12-12

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